CN113583440B - Nylon 66 material and preparation method thereof - Google Patents
Nylon 66 material and preparation method thereof Download PDFInfo
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- CN113583440B CN113583440B CN202111125954.1A CN202111125954A CN113583440B CN 113583440 B CN113583440 B CN 113583440B CN 202111125954 A CN202111125954 A CN 202111125954A CN 113583440 B CN113583440 B CN 113583440B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a nylon 66 material and a preparation method thereof, belonging to the technical field of high polymer materials. The nylon 66 material comprises the following components in percentage by weight: PA 6627% -86.7%, first flashing inhibitor 0.1% -1%, second flashing inhibitor 3% -10%, glass fiber 10% -60%, antioxidant 0.1% -1%, and lubricant 0.1% -1%, wherein the second flashing inhibitor is aromatic polyamide. According to the invention, the aromatic polyamide is used as the second flashing inhibitor, and the characteristics of rigid benzene ring in the molecule of the aromatic polyamide, relatively high crystallization temperature, good compatibility with PA66 and the like are utilized, so that the aromatic polyamide can be intertwined with a PA66 molecular chain, can flow well, can be rapidly molded, and can greatly inhibit the generation of flashing.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a nylon 66 material and a preparation method thereof.
Background
Polyamides (PA, nylon) are assemblies of polymers containing amide groups in the repeating units of the macromolecular main chain. The polyamide has the characteristics of good comprehensive properties including mechanical property, heat resistance, wear resistance, chemical resistance and self-lubricity, low friction coefficient, certain flame retardance, easiness in processing and the like, so that the polyamide becomes a polymer material with the widest application and the largest variety in the engineering plastic industry. The varieties of PA are PA6, PA66, PA11, PA12, PA46, PA610, PA612 and PA PAl010, semi-aromatic nylon PA6T, special nylon and the like.
Polyamide 66 or nylon 66 (PA 66), obtained by polycondensation of adipic acid and hexamethylenediamine, is a crystalline polymer in the form of particles which is translucent or opaque, milky-white or yellowish. Because of its excellent mechanical, heat-resistant, wear-resistant, self-lubricating, low-temperature resistant and fire-retardant properties, it is widely used in the automobile industry, instrument housings and other products requiring impact resistance and high strength. In actual production, the flowability of the PA66 material is always a concern in the injection molding process. The PA66 material has good fluidity, so when the PA66 material is used for injection molding of a large part or a thin-wall part, due to the factors of complex mold, high injection molding temperature and the like, the PA66 can easily flow into a fine gap of the mold, and the phenomena of flash, flash and the like are generated, so that the normal injection molding production efficiency is influenced, the reject ratio of the product is improved, the subsequent trimming flash procedure is increased, and meanwhile, certain damage is caused to the mold.
At present, a commonly used solution for the glass fiber reinforced PA66 material is to increase the proportion of filler (such as glass fiber) in the PA66 material or increase the viscosity (i.e., relative molecular weight) of PA66 to inhibit the flashing problem. However, on one hand, increasing the proportion of the filler leads to an increase in the density of the PA66 material, which affects the toughness of the product, while the high-viscosity PA66 has a higher torque during modified extrusion, which leads to a great reduction in processing efficiency, and on the other hand, the effect of reducing flash is limited in both methods.
Therefore, it is desirable to provide a new PA66 material to solve the above problems.
Disclosure of Invention
In order to solve the problems in the prior art, the embodiment of the invention provides a novel nylon 66 material to overcome the problems that the PA66 in the prior art is easy to flow into a fine gap of a mold during injection molding, and flash are generated.
In order to solve one or more of the above technical problems, the present application adopts the following technical solutions:
in one aspect, a nylon 66 material is provided, and the nylon 66 material comprises the following components in percentage by weight:
PA 6627% -86.7%, first flash inhibitor 0.1% -1%, second flash inhibitor 3% -10%, glass fiber 10% -60%, antioxidant 0.1% -1%, and lubricant 0.1% -1%, wherein the second flash inhibitor is aromatic polyamide.
Further, the ratio of the first flashing inhibitor to the second flashing inhibitor is 1: 10-1: 90.
Further, the nylon 66 material comprises the following components in percentage by weight:
PA 6637.4% -79.4%, first flashing inhibitor 0.2% -1%, second flashing inhibitor 5% -10%, glass fiber 15% -50%, antioxidant 0.2% -0.8% and lubricant 0.2% -0.8%, wherein the second flashing inhibitor is aromatic polyamide.
Further, the nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, talcum powder 0.3%, PA 6T/665%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%.
Further, the aromatic polyamide comprises one or more of PA66/6T, PA6T/66, PA6T/6, PA6T/66/6 and PA 6T/6I.
Further, the first flashing inhibitor is a nucleating agent.
Further, the nucleating agent comprises one or more of talcum powder, montmorillonite, calcium carboxylate, phenylphosphinate, P22, wollastonite, alumina, barium sulfate, hydrotalcite, kaolin, attapulgite and calcium fluoride.
Further, the relative sulfuric acid viscosity of the PA66 is 2.1-3.8.
Further, the antioxidant comprises one or more of antioxidant 168, antioxidant 1010 and antioxidant 1098.
Further, the lubricant is one or more of calcium stearate, stearic acid, ethylene bis stearamide, pentaerythritol stearate, silicone powder and polyethylene wax.
In another aspect, a method for preparing a nylon 66 material is provided, the method comprising:
preparing raw materials according to the following weight percentages:
PA 6627% -86.7%, first flashing inhibitor 0.1% -1%, second flashing inhibitor 3% -10%, glass fiber 10% -60%, antioxidant 0.1% -1%, and lubricant 0.1% -1%;
uniformly mixing the PA66, the first flashing inhibitor, the second flashing inhibitor, the antioxidant and the lubricant through a mixer, adding the mixture into a double-screw extruder for blending, adding glass fiber through lateral feeding, cooling extruded strips through a water tank, wherein the temperature of cooling water is 15-20 ℃, granulating through a granulator, and drying to obtain the nylon 66 material, wherein the rotation speed of the granulator is 500-700 rpm.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
according to the nylon 66 material and the preparation method thereof provided by the embodiment of the invention, the first flashing inhibitor and the second flashing inhibitor are added into the glass fiber reinforced PA66 system, on one hand, the second flashing inhibitor adopts aromatic polyamide, and the characteristics of rigid benzene ring in the molecule of the aromatic polyamide, relatively high crystallization temperature, good compatibility with PA66 and the like are utilized, so that the second flashing inhibitor can be intertwined with the PA66 molecular chain, can flow well and can be rapidly molded, and the generation of flashing is greatly inhibited, on the other hand, the second flashing inhibitor plays a main role in inhibiting flashing, the first flashing inhibitor performs a synergistic effect, and the first flashing inhibitor and the second flashing inhibitor can generate a synergistic effect by compounding, so that the nucleation speed is further increased under the condition that the second flashing inhibitor is added, the crystallization process is accelerated, and the generation of flashing is further reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a nylon 66 material provided in the examples of the present application;
fig. 2 is a schematic structural diagram of a rectangular parallelepiped test strip mold provided in an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As described in the background art, the PA66 in the prior art is liable to flow into the fine gap of the mold during injection molding, and has problems such as flash and flash. In order to solve the problem, the invention provides a novel nylon 66 material, which is prepared by adding a first flashing inhibitor and a second flashing inhibitor into a glass fiber reinforced PA66 system (namely adding a proper amount of glass fibers into polyamide to enhance rigidity), wherein the first flashing inhibitor can adopt a nucleating agent, and the second flashing inhibitor can adopt aromatic polyamide. The nucleating agent can improve the cooling and nucleating speed of the glass fiber reinforced PA66 melt after being injected into the mold and contacting with the mold wall, so that the melt is rapidly solidified, the melt is inhibited from flowing out from the mold gap, and the flash phenomenon is reduced. The aromatic polyamide has rigid benzene rings in molecules, has relatively high crystallization temperature and good compatibility with PA66, can be intertwined with PA66 molecular chains, can flow well and be quickly molded, and greatly inhibits the generation of flash.
In a preferred embodiment, the ratio of the first flashing inhibitor to the second flashing inhibitor is 1:10 to 1: 90.
Specifically, in the embodiment of the invention, although the first flashing inhibitor and the second flashing inhibitor have certain effects when used alone, when the first flashing inhibitor and the second flashing inhibitor are compounded and used according to any proportion of 1: 10-1: 90, a synergistic effect can be generated, flashing is further reduced, the effect of inhibiting flashing tends to be stable, and if the proportion is continuously increased, the mechanical property of the glass fiber reinforced PA66 material is affected. Preferably, in the embodiment of the present invention, on the premise of not affecting other properties of the nylon 66 material, the ratio of the first flashing inhibitor to the second flashing inhibitor is 1: 16.7.
In the embodiment of the present invention, the nylon 66 material comprises the following components by weight:
PA 6637.4% -79.4%, first flashing inhibitor 0.2% -1%, second flashing inhibitor 5% -10%, glass fiber 15% -50%, antioxidant 0.2% -0.8% and lubricant 0.2% -0.8%, wherein the second flashing inhibitor is aromatic polyamide.
In the embodiment of the present invention, the nylon 66 material comprises the following components by weight:
PA 6664.1%, talcum powder 0.3%, PA 6T/665%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%.
Specifically, when the nylon 66 material is prepared according to the proportion of the components, the effect of suppressing the flash is better, and other properties are not affected. Preferably, the first flashing inhibitor is talc with a mesh number of 2000-30000 and the second flashing inhibitor is PA 6T/66.
As a preferred embodiment, in the examples of the present invention, the aromatic polyamide comprises one or more of PA66/6T, PA6T/66, PA6T/6, PA6T/66/6 and PA 6T/6I.
Specifically, aromatic polyamide (aramid for short) is a synthetic fiber prepared by polycondensation spinning of an aromatic material. The fiber has good heat resistance and insulating property, stable working chemical property and good resistance to weak acid, weak base and most organic solvents. The aromatic polyamide includes, but is not limited to, PA66/6T, PA6T/66, PA6T/6, PA6T/66/6, PA6T/6I, etc., and when used as a second flashing inhibitor, the aromatic polyamide may be a mixture of one or more of the above components. Preferably, the second flashing inhibitor employs PA 6T/66. Because the molecules of the aromatic polyamide are provided with rigid benzene rings, the crystallization temperature is relatively high, and the aromatic polyamide has good compatibility with PA66, can be intertwined with PA66 molecular chains, can flow well, can be quickly molded, and greatly inhibits the generation of flash.
Specifically, in the embodiment of the present invention, the weight percentage of the second flashing inhibitor is in a range of 3% to 10%, and preferably, the weight percentage of the second flashing inhibitor is 5%.
In one preferred embodiment, the first flashing inhibitor is a nucleating agent.
In particular, the nucleating agent can improve the physical and mechanical properties such as shortening the molding cycle, improving the transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and the like of the product by changing the crystallization behavior of the resin, accelerating the crystallization rate, increasing the crystallization density and promoting the grain size to be micronized. In the implementation of the invention, the nucleating agent and the aromatic polyamide are added into a glass fiber reinforced PA66 system according to a certain proportion and are jointly used as a flash inhibitor, on one hand, the characteristics of the nucleating agent are utilized to improve the speed of injecting the glass fiber reinforced PA66 melt into a mould and cooling and nucleating the melt by contacting with the mould wall, so that the melt is rapidly solidified and the melt is inhibited from flowing out from the mould gap, on the other hand, the nucleating agent can generate a synergistic effect with the aromatic polyamide, and further the generation of flash is reduced.
Specifically, in the embodiment of the present invention, the weight percentage of the first flashing inhibitor is in a range of 0.1% to 1%, and preferably, the weight percentage of the first flashing inhibitor is 0.3%.
In a preferred embodiment, the nucleating agent comprises one or more of talc, montmorillonite, calcium carboxylate, phenylphosphinate, and calcium fluoride.
Specifically, nucleating agents include, but are not limited to, talc, montmorillonite, calcium carboxylate, phenylphosphinate, P22 (Nylon 22), wollastonite, alumina, barium sulfate, hydrotalcite, kaolin, attapulgite, calcium fluoride, and the like. In the embodiment of the present invention, the nucleating agent used as the first flashing inhibitor may be a mixture of one or more of the above-mentioned components. Preferably, the first flash inhibitor adopts talcum powder, the mesh number of the talcum powder is any value in [2000-30000], and the mesh number of the talcum powder is 20000.
In a preferred embodiment of the present invention, the PA66 has a relative sulfuric acid viscosity of 2.1 to 3.8.
Specifically, the relative sulfuric acid viscosity of PA66 may characterize the relative molecular weight of PA66, with the greater the relative sulfuric acid viscosity, the greater the molecular weight, and the smaller the flash. Preferably, the relative sulfuric acid viscosity of PA66 is 2.4.
In a preferred embodiment, the antioxidant comprises one or more of antioxidant 168, antioxidant 1010 and antioxidant 1098.
In particular, the thermal oxidation reaction speed and the thermal oxidation reaction resistance of the plastic resin are greatly different due to different molecular structures, or different polymerization processes, different processing processes, different use environments and different conditions of the same molecular structure. The antioxidant is added into the plastic resin as a plastic additive, so that the thermal oxidation reaction speed of plastic macromolecules can be effectively inhibited or reduced, the thermal and oxygen degradation process of the plastic resin is delayed, the heat resistance of the plastic resin is obviously improved, the service life of a plastic product is prolonged, and the use value of the plastic product is improved.
Specifically, in the embodiment of the present invention, the antioxidant includes, but is not limited to, antioxidant 168, antioxidant 1010, antioxidant 1098, and the like, and in the implementation, one or more of the above antioxidants may be used, which is not limited herein. In addition, in the embodiment of the present invention, the weight percentage of the antioxidant is in the range of 0.1% to 1%, and preferably, the weight percentage of the antioxidant is 0.3%.
In the present embodiment, the lubricant is one or more of calcium stearate, stearic acid, ethylene bis-stearamide, pentaerythritol stearate, silicone powder, and polyethylene wax.
In particular, PA66 often has problems with rough, low gloss or flow marks and exposed glass fibers during processing due to excessive melt viscosity. In order to solve these problems, a lubricant is usually added during the preparation process, and may have a polar group structure combined with a part of polar groups on the surface of the glass fiber, so as to improve the bonding state of the glass fiber and the reinforced PA66 particle resin, and further improve the dispersibility of the resin. The lubricant is added to enhance the lubricating property, improve the processing fluidity of the glass fiber reinforced nylon and improve the surface smoothness of the material. In addition, the addition of lubricants can have an effect on the appearance of the reinforced nylon article. When the melt flows in the die cavity, due to the fact that the thickness of the melt is not uniform, the resistance is different, the flowing space at the position of a thin interface is small, the resistance is large, the flowing speed is low, and during forming, due to the fact that the melt is stressed, glass fibers can migrate to the surface to cause the situation that the glass fibers are exposed.
Specifically, in the embodiment of the present invention, the lubricant includes, but is not limited to, calcium stearate, stearic acid, ethylene bis-stearamide, pentaerythritol stearate, silicone powder, polyethylene wax, and the like, and when implemented, one or more of the foregoing may be selected. Specifically, in the embodiment of the present invention, the weight percentage of the lubricant is in the range of 0.1% to 1%, and preferably, the weight percentage of the lubricant is 0.3%.
It should be noted that, in addition to the above components, the components of the nylon 66 material in the embodiment of the present application may also be added with other processing aids according to actual processing requirements, so as to improve the performance of the nylon 66 material, where no specific limitation is made to the other processing aids, and a user may select the processing aids according to the actual requirements.
Corresponding to the nylon 66 material, an embodiment of the present invention further provides a preparation method of the nylon 66 material, and as shown in fig. 1, the method includes the following steps:
s1: preparing raw materials according to the following weight percentages:
PA 6627% -86.7%, first flashing inhibitor 0.1% -1%, second flashing inhibitor 3% -10%, glass fiber 10% -60%, antioxidant 0.1% -1%, and lubricant 0.1% -1%;
s2: uniformly mixing the PA66, the first flash inhibitor, the second flash inhibitor, the antioxidant and the lubricant by a mixer, and adding the mixture into a double-screw extruder for blending;
s3: adding glass fiber through lateral feeding, and cooling the extruded material strip through a water tank, wherein the temperature of cooling water is 15-20 ℃;
s4: and (3) granulating by using a granulator and drying to obtain the nylon 66 material, wherein the rotating speed of the granulator is 500-700 rpm.
All the above-mentioned optional technical solutions can be combined arbitrarily to form the optional embodiments of the present invention, and are not described herein again.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Comparative example 1
A nylon 66 material comprises the following components in percentage by weight:
PA 6627%, glass fiber 72.4%, antioxidant 0.3%, and lubricant 0.3%, wherein PA66 has relative sulfuric acid viscosity of 2.4.
Comparative example 2
A nylon 66 material comprises the following components in percentage by weight:
PA 6639.4%, glass fiber 60%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Comparative example 3
A nylon 66 material comprises the following components in percentage by weight:
PA 6656.8%, glass fiber 42.6%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Comparative example 4
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, glass fiber 35.3%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Comparative example 5
A nylon 66 material comprises the following components in percentage by weight:
PA 6669.4%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Comparative example 6
A nylon 66 material comprises the following components in percentage by weight:
PA 6686.7%, glass fiber 12.7%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Comparative example 7
A nylon 66 material comprises the following components in percentage by weight:
PA 6689.4%, glass fiber 10%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Comparative example 8
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, glass fiber 35.3%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.1.
Comparative example 9
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, glass fiber 35.3%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.7.
Comparative example 10
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, glass fiber 35.3%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 3.2.
Example 1
A nylon 66 material comprises the following components in percentage by weight:
PA 6666.4%, PA6T/66 (second flashing inhibitor) 3%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein PA66 has a relative sulfuric acid viscosity of 2.4.
Example 2
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.4%, PA6T/66 (second flashing inhibitor) 5%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 3
A nylon 66 material comprises the following components in percentage by weight:
PA 6662.4%, PA6T/66 (second flashing inhibitor) 7%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 4
A nylon 66 material comprises the following components in percentage by weight:
PA 6659.4%, PA6T/66 (second flashing inhibitor) 10%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 5
A nylon 66 material comprises the following components in percentage by weight:
PA 6669.3%, talcum powder (first flash inhibitor) 0.1%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 6
A nylon 66 material comprises the following components in percentage by weight:
PA 6669.1%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 7
A nylon 66 material comprises the following components in percentage by weight:
PA 6668.8%, talcum powder (first flash inhibitor) 0.6%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 8
A nylon 66 material comprises the following components in percentage by weight:
PA 6668.4%, talcum powder (first flash inhibitor) 1%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 9
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.3%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.1%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 10
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 11
A nylon 66 material comprises the following components in percentage by weight:
PA 6663.8%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.6%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 12
A nylon 66 material comprises the following components in percentage by weight:
PA 6663.4%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 1%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 13
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.3%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.1% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 14
A nylon 66 material comprises the following components in percentage by weight:
PA 6663.9%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.5% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 15
A nylon 66 material comprises the following components in percentage by weight:
PA 6663.4%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 1% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 16
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.3%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.1%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 17
A nylon 66 material comprises the following components in percentage by weight:
PA 6663.9%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.5%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 18
A nylon 66 material comprises the following components in percentage by weight:
PA 6663.4%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 1%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 19
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA66/6T (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 20
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 21
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/6 (second flash inhibitor) 5%, talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 22
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flashing inhibitor) 5%, montmorillonite (first flashing inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 23
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flashing inhibitor) 5%, calcium carboxylate (first flashing inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein PA66 has a relative sulfuric acid viscosity of 2.4.
Example 24
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, 2000-mesh talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 25
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, 4000 mesh talc powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 26
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, 10000 meshes of talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 27
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, 20000 mesh talc powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3%, and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Example 28
A nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, PA6T/66 (second flash inhibitor) 5%, 30000 mesh talcum powder (first flash inhibitor) 0.3%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%, wherein the relative sulfuric acid viscosity of PA66 is 2.4.
Wherein, the PA66 related to the above comparative example and the embodiment can adopt PA66 product sold by Henan Shenma nylon New materials GmbH, the ECS301HP-3-H, PA6T/66 of glass fiber sold by Chongqing International composite materials GmbH can adopt HTPA 1245 sold by Qingdao Sanliuo New materials GmbH, the PA6T/6 of glass fiber sold by Qingdao Sanliuo New materials GmbH can adopt HTPA 1145 sold by Qingdao Sanliuo New materials GmbH, the talcum powder can adopt talcum powder product sold by Asaho powder raw materials GmbH, the calcium carboxylate can adopt CAV102 sold by Clalaine chemical (China) GmbH, the montmorillonite can adopt 4 sold by Zhejiang Hongyo New materials GJH, the antioxidant can adopt S222 2225P sold by Yabao, and the lubricant can adopt EBS sold by Longsha.
Fig. 2 is a schematic structural diagram of a rectangular parallelepiped test strip mold provided in an embodiment of the present application, and referring to fig. 2, in order to compare and simulate the flash generated in actual injection molding, the present invention uses a rectangular parallelepiped test strip mold of 140mm by 10mm by 0.4mm, a slit of 10mm by 5mm by 0.05mm is processed at the end of the test strip, and the flash overflowing from the slit is used to characterize the flash of the glass fiber reinforced PA66 material.
Specifically, the nylon 66 material of comparative examples 1 to 10 and examples 1 to 28 was melted and poured into a rectangular parallelepiped test bar mold, and after cooling, the dimensions of the flash were measured, respectively, as follows:
TABLE 1 results of the determination of the nylon 66 materials of comparative examples 1-10 and examples 1-18
| PA66 | Relative sulfuric acid viscosity | PA6T/66 | Talcum powder | Glass fiber | Antioxidant agent | Lubricant agent | Flash length mm | |
| Comparative example 1 | 27% | 2.4 | 0 | 0 | 72.4% | 0.3% | 0.3% | 2.70 |
| Comparative example 2 | 39.4% | 2.4 | 0 | 0 | 60% | 0.3% | 0.3% | 2.67 |
| Comparative example 3 | 56.8% | 2.4 | 0 | 0 | 42.6% | 0.3% | 0.3% | 3.12 |
| Comparative example 4 | 64.1% | 2.4 | 0 | 0 | 35.3% | 0.3% | 0.3% | 3.27 |
| Comparative example 5 | 69.4% | 2.4 | 0 | 0 | 30% | 0.3% | 0.3% | 3.36 |
| Comparative example 6 | 86.7% | 2.4 | 0 | 0 | 12.7% | 0.3% | 0.3% | 3.54 |
| Comparative example 7 | 89.4% | 2.4 | 0 | 0 | 10% | 0.3% | 0.3% | 3.61 |
| Comparative example 8 | 64.1% | 2.1 | 0 | 0 | 35.3% | 0.3% | 0.3% | 3.56 |
| Comparative example 9 | 64.1% | 2.7 | 0 | 0 | 35.3% | 0.3% | 0.3% | 3.13 |
| Comparative example 10 | 64.1% | 3.2 | 0 | 0 | 35.3% | 0.3% | 0.3% | 2.97 |
| Example 1 | 66.4% | 2.4 | 3% | 0 | 30% | 0.3% | 0.3% | 1.05 |
| Example 2 | 64.4% | 2.4 | 5% | 0 | 30% | 0.3% | 0.3% | 0.57 |
| Example 3 | 62.4% | 2.4 | 7% | 0 | 30% | 0.3% | 0.3% | 0.55 |
| Example 4 | 59.4% | 2.4 | 10% | 0 | 30% | 0.3% | 0.3% | 0.54 |
| Example 5 | 69.3% | 2.4 | 0 | 0.1% | 30% | 0.3% | 0.3% | 3.16 |
| Example 6 | 69.1% | 2.4 | 0 | 0.3% | 30% | 0.3% | 0.3% | 2.88 |
| Example 7 | 68.8% | 2.4 | 0 | 0.6% | 30% | 0.3% | 0.3% | 2.85 |
| Example 8 | 68.4% | 2.4 | 0 | 1% | 30% | 0.3% | 0.3% | 2.84 |
| Example 9 | 64.3% | 2.4 | 5% | 0.1% | 30% | 0.3% | 0.3% | 0.43 |
| Example 10 | 64.1% | 2.4 | 5% | 0.3% | 30% | 0.3% | 0.3% | 0.27 |
| Example 11 | 63.8% | 2.4 | 5% | 0.6% | 30% | 0.3% | 0.3% | 0.25 |
| Example 12 | 63.4% | 2.4 | 5% | 1% | 30% | 0.3% | 0.3% | 0.26 |
| Example 13 | 64.3% | 2.4 | 5% | 0.3% | 30% | 0.1% | 0.3% | 0.27 |
| Example 14 | 63.9% | 2.4 | 5% | 0.3% | 30% | 0.5% | 0.3% | 0.26 |
| Example 15 | 63.4% | 2.4 | 5% | 0.3% | 30% | 1% | 0.3% | 0.27 |
| Example 16 | 64.3% | 2.4 | 5% | 0.3% | 30% | 0.3% | 0.1% | 0.27 |
| Example 17 | 63.9% | 2.4 | 5% | 0.3% | 30% | 0.3% | 0.5% | 0.28 |
| Example 18 | 63.4% | 2.4 | 5% | 0.3% | 30% | 0.3% | 1% | 0.31 |
From the test data in table 1 above, it can be seen that:
1. as can be seen from the test data of comparative examples 1 to 7, increasing the proportion of the glass fiber can inhibit the flash to a certain extent, and the trend of the inhibition on the flash becomes slower with the increase of the proportion of the glass fiber. In view of both shrinkage and density of the article, a 30% glass fiber ratio is preferred. As can be seen from the test data of comparative examples 1 to 7 and examples 1 to 18, the effect of suppressing flashing by increasing the proportion of glass fibers is obviously not as good as that of adding a flashing inhibitor (including a first flashing inhibitor and/or a second flashing inhibitor);
2. from the test data of comparative examples 8 to 10, it can be seen that increasing the relative sulfuric acid viscosity of PA66 can also inhibit the flash to some extent, further increase the relative sulfuric acid viscosity, and the inhibition effect on the flash is increased to a limited extent. As can be seen from the test data of comparative examples 8 to 10 and examples 1 to 18, the effect of increasing the relative sulfuric acid viscosity of PA66 in suppressing flashing is also good without adding a flashing inhibitor (including the first flashing inhibitor and/or the second flashing inhibitor);
3. it can be seen from the test data of examples 1 to 12 that the second flashing inhibitor has a main flashing inhibition effect, the first flashing inhibitor has a certain synergistic effect, and the flashing inhibition effect when the second flashing inhibitor and the first flashing inhibitor are used together is obviously better than that when one of the second flashing inhibitors is used alone, and further, referring to the test data of examples 1 to 4, when the second flashing inhibitor is used alone, on the premise of ensuring other performances of the nylon 66 material, the effect of suppressing flashing is better when the weight percentage of the second flashing inhibitor is 3% to 10%, and the improvement of the flashing inhibition effect by increasing the proportion is limited. Further referring to the test data of examples 5 to 8, it can be seen that when the weight percentage of the first flashing inhibitor is 0.1% to 1%, the flashing inhibition effect is better, and the improvement of the flashing inhibition effect by increasing the ratio is limited. On the premise of ensuring other performances of the nylon 66 material, when the ratio of the second flashing inhibitor to the first flashing inhibitor is 16.7:1, the effect of the second flashing inhibitor and the first flashing inhibitor for synergistically inhibiting flashing is better;
4. from the test data of examples 13 to 18, it can be seen that the change in the weight percentage of the antioxidant and the lubricant has little effect on the flash suppression effect.
TABLE 2 determination of the nylon 66 materials of examples 19-23
| PA66 | Relative sulfuric acid viscosity | Second flashing inhibitor (5%) | First flashing inhibitor (0.3%) | Glass fiber | Antioxidant agent | Lubricant agent | Flash length mm | |
| Example 19 | 64.1% | 2.4 | PA66/6T | Talcum powder | 30% | 0.3% | 0.3% | 0.57 |
| Example 20 | 64.1% | 2.4 | PA6T/66 | Talcum powder | 30% | 0.3% | 0.3% | 0.27 |
| Example 21 | 64.1% | 2.4 | PA6T/6 | Talcum powder | 30% | 0.3% | 0.3% | 0.43 |
| Example 22 | 64.1% | 2.4 | PA6T/66 | Montmorillonite clay | 30% | 0.3% | 0.3% | 0.35 |
| Example 23 | 64.1% | 2.4 | PA6T/66 | Carboxylic acid calcium salt | 30% | 0.3% | 0.3% | 0.42 |
From the test data in table 2 above, it can be seen that:
from the test data of examples 19 to 23, it is found that the burr suppressing effect is the most excellent when the second burr suppressing agent is PA6T/66, and the burr suppressing effect is the most excellent when the first burr suppressing agent is talc.
TABLE 3 determination of the Nylon 66 materials of examples 24-28
| PA66 | Relative sulfuric acid viscosity | PA6T/66 | Talcum powder mesh number (0.3%) | Glass fiber | Antioxidant agent | Lubricant agent | Flash length mm | |
| Example 24 | 64.1% | 2.4 | 5% | 2000 | 30% | 0.3% | 0.3% | 0.54 |
| Example 25 | 64.1% | 2.4 | 5% | 4000 | 30% | 0.3% | 0.3% | 0.52 |
| Example 26 | 64.1% | 2.4 | 5% | 10000 | 30% | 0.3% | 0.3% | 0.45 |
| Example 27 | 64.1% | 2.4 | 5% | 20000 | 30% | 0.3% | 0.3% | 0.27 |
| Example 28 | 64.1% | 2.4 | 5% | 30000 | 30% | 0.3% | 0.3% | 0.31 |
From the test data in table 3 above, it can be seen that:
from the test data of examples 24 to 28, it is found that the mesh number of talc has a certain influence on the burr-suppressing effect, and the burr-suppressing effect is most excellent when the mesh number of talc is 20000.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A nylon 66 material is characterized in that the nylon 66 material comprises the following components in percentage by weight:
PA 6627% -86.7%, first flashing inhibitor 0.1% -1%, second flashing inhibitor 3% -10%, glass fiber 10% -60%, antioxidant 0.1% -1%, and lubricant 0.1% -1%, wherein the second flashing inhibitor is aromatic polyamide, the aromatic polyamide comprises one or more of PA66/6T, PA6T/66, PA6T/6, and PA6T/66/6, and the first flashing inhibitor is a nucleating agent.
2. The nylon 66 material of claim 1, wherein the ratio of the first flashing inhibitor to the second flashing inhibitor is from 1:10 to 1: 90.
3. The nylon 66 material of claim 1 or 2, wherein the nylon 66 material comprises the following components in percentage by weight:
PA 6637.4% -79.4%, first flashing inhibitor 0.2% -1%, second flashing inhibitor 5% -10%, glass fiber 15% -50%, antioxidant 0.2% -0.8% and lubricant 0.2% -0.8%, wherein the second flashing inhibitor is aromatic polyamide.
4. The nylon 66 material of claim 1 or 2, wherein the nylon 66 material comprises the following components in percentage by weight:
PA 6664.1%, nucleating agent talcum powder 0.3%, PA 6T/665%, glass fiber 30%, antioxidant 0.3% and lubricant 0.3%.
5. The nylon 66 material of claim 1, wherein the nucleating agent comprises one or more of talc, montmorillonite, calcium carboxylate, phenylphosphinate, P22, wollastonite, alumina, barium sulfate, hydrotalcite, kaolin, attapulgite, calcium fluoride.
6. The nylon 66 material of claim 1 or 2, wherein the relative sulfuric acid viscosity of the PA66 is 2.1-3.8.
7. The nylon 66 material of claim 1 or claim 2, wherein the antioxidant comprises one or more of antioxidant 168, antioxidant 1010, and antioxidant 1098.
8. The nylon 66 material of claim 1 or 2, wherein the lubricant is one or more of calcium stearate, stearic acid, ethylene bis stearamide, pentaerythritol stearate, silicone powder, polyethylene wax.
9. A method for preparing a nylon 66 material, which is used for preparing the nylon 66 material of claim 1, and comprises the following steps:
preparing raw materials according to the following weight percentages:
PA 6627% -86.7%, first flashing inhibitor 0.1% -1%, second flashing inhibitor 3% -10%, glass fiber 10% -60%, antioxidant 0.1% -1%, and lubricant 0.1% -1%, wherein the second flashing inhibitor is aromatic polyamide, the aromatic polyamide comprises one or more of PA66/6T, PA6T/66, PA6T/6, PA6T/66/6, and the first flashing inhibitor is a nucleating agent;
uniformly mixing the PA66, the first flashing inhibitor, the second flashing inhibitor, the antioxidant and the lubricant through a mixer, adding the mixture into a double-screw extruder for blending, adding glass fiber through lateral feeding, cooling extruded strips through a water tank, wherein the temperature of cooling water is 15-20 ℃, granulating through a granulator, and drying to obtain the nylon 66 material, wherein the rotation speed of the granulator is 500-700 rpm.
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